TW493012B - Apparatus for and method of manufacturing plastic container coated with carbon film - Google Patents
Apparatus for and method of manufacturing plastic container coated with carbon film Download PDFInfo
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- TW493012B TW493012B TW084107275A TW84107275A TW493012B TW 493012 B TW493012 B TW 493012B TW 084107275 A TW084107275 A TW 084107275A TW 84107275 A TW84107275 A TW 84107275A TW 493012 B TW493012 B TW 493012B
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32348—Dielectric barrier discharge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/08—Plant for applying liquids or other fluent materials to objects
- B05B5/12—Plant for applying liquids or other fluent materials to objects specially adapted for coating the interior of hollow bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
- B05D7/227—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of containers, cans or the like
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D23/00—Details of bottles or jars not otherwise provided for
- B65D23/02—Linings or internal coatings
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45563—Gas nozzles
- C23C16/45578—Elongated nozzles, tubes with holes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32082—Radio frequency generated discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/32—Processing objects by plasma generation
- H01J2237/33—Processing objects by plasma generation characterised by the type of processing
- H01J2237/332—Coating
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Analytical Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Chemical Vapour Deposition (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
經濟部中央標準局員工消費合作社印製 493012 A7 B7 五、發明説明(t ) [發明之領域] 本發明係關於用硬質碳膜塗膜内壁面之塑膠容器之製造 裝置及製法。 [發明之背景] 一般而言,塑膠容器,係由於其容易成形及輕量性,成 本低等名種特性,在食品領域及翳藥品領域等之各種領域 中泛地做為包裝容器使用。 然而,塑膠具有使氧及二氧化碳等低分子氣體透過之性 質,再者,低分子有機化合物吸附於內部之性質,塑膠容 器與玻璃等其他容器比較,其使用對象及使用形態I受到 各種限制。 在此所謂吸附者,係指低分子有機化合物滲透而擴散於 塑膠之組成中而吸收於塑膠中而言。 例如,將啤酒等碳酸飮料填充於塑膠容器內時,内容物 之飲料,由於透過塑膠而滲透於容器内部之f ,經過一段 時間引起$化而劣化,或碳酸氣體透過塑膠而 放出於器 外部,使碳酸飲料成為洩了氣之飲料。 又,具有橘汁等香料成分之飲料填充於塑膠飲料容器時 ,含在飲料內之低分子有機化合物之香料成份(例如橘汁 之檸檬烯等)為由塑膠所吸附,破壞飲料之香料成份組成 平衡,有飲料品質劣化之0形。 又,塑膠容器之組成中所含有之低分子化合物之溶出成 為問題。即,塑膠容器內填充要求純度(尤其是液體)時, 含在塑膠組成中之可塑劑及殘留單體,及其他之添加劑溶 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 4 - (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 493012 A7 B7 V. Description of the Invention (t) [Field of Invention] The present invention relates to a manufacturing device and a manufacturing method for a plastic container coated with a hard carbon film on the inner wall surface. [Background of the Invention] Generally speaking, plastic containers are widely used as packaging containers in various fields such as the food field and the pharmaceutical industry because of their easy-to-form, lightweight, and low-cost characteristics. However, plastic has the property of permeating low-molecular gases such as oxygen and carbon dioxide. In addition, low-molecular organic compounds are adsorbed inside. Compared with other containers such as glass, plastic containers are subject to various restrictions on their use and form I. The term "adsorber" refers to a case where a low-molecular organic compound permeates and diffuses into a plastic composition and is absorbed in the plastic. For example, when carbonated materials such as beer are filled in a plastic container, the contents of the beverage, because they penetrate the inside of the container through plastic, will deteriorate over time, or carbonated gas will be released outside the container through plastic. Make carbonated drinks a discouraged drink. In addition, when a beverage with flavor components such as orange juice is filled in a plastic beverage container, the flavor components (such as limonene in orange juice) of the low-molecular organic compounds contained in the beverage are adsorbed by the plastic, which destroys the balance of flavor components of the beverage , There is no shape of beverage quality deterioration. In addition, the dissolution of low-molecular compounds contained in the composition of the plastic container becomes a problem. That is, when the plastic container is filled with a purity (especially a liquid), the plasticizer and residual monomers contained in the plastic composition, and other additives are dissolved. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). _ 4-(Please read the notes on the back before filling this page)
493012 A7 B7 五、發明説明(2 進 題 問 會 。 社 性為 能成 可收 之 回 度 之 純器 物容 容過 内用 及使 損 , 有在 ’ 現 中 , 物面 容方 内 一 於另 出 器被 容 , 充内 填間 再期 為之 做收 器回 容 至 膠後 塑用 將使 欲在 而器 然容 , 璃 化玻 環於 循 異 再但 之 , 源用 資 使 行而 吸後 物淨 合洗 化在 機, 有物 子合 份化 低機 種有 各子 等分 臭低 霉 之 有附 ’ 吸 時該 中 .0 境 内 環器 然容 自膠 於塑 置在 放附 使溶 ο 而地題 器慢問 容 慢之 充而上 填份生 再成衛 為異及 做為低 器成降 容 物質 膠 合 品 塑化之 將機物 , 有 容 此子内 因分發 , 低 引 內 之 , 膠附内 塑吸物 在所容 留 , 内 然時於 仍用出 及提 質K 性向 ο 之 定 之過膠 用透塑 使體使 器 氣 而 容子 , 還 分 質 退低性 可使之 為 之 剖 做器内 未容於 β 0 【 toe: 幾塑吸 為 之 物 器述合 容 hib 膠如機 塑制有 , 抑子 此為分 因 低 之完 等 , 膜下 薄態 鋁狀 或的 膠性 塑特 之 之 低 器 更 容 。 性膠題 附塑問 吸 特之 合 維附 層在吸 用法及 使 無 性 或均擋 ,, 胆 度而體 ib然氣 晶 ,決 結法解 高 方全 實 之 等 瓶 燒 及 杯 燒 1a覆 ?塗 碳CB 之DL 0 幵 石 , 剛琨 金出 c(術 DL技 有 成 , 形 來膜 阼 薄 近 之 膜 η r Γ a (請先閱讀背面之注意事項再填寫本頁)493012 A7 B7 V. Explanation of the invention (2 Questions and answers to questions. The social nature of pure utensils that can be receivable can be used for internal use and damage. It will be filled, and the filling and filling room will be used as the receiver. After the plastic is filled, the plastic will be used, and the glass will be used in different ways. Net combination washing and washing machine, there is a combination of material and low unit types have halves of odor and mildew, and it is attached when it is sucked. 0 The domestic ring device is self-adhesive and placed in plastic to dissolve. The question is slowly filled with content, and then filled with fresh ingredients, then it is different, and as a low device, it is a plastic material that reduces the volume of the glue. The plastic object is contained in this container because of its distribution. The plastic absorbent is contained in it, but it is still used and the quality is improved. The plastic is used to make the body gas and the container, and it can also be used as a dissection device. The content is not contained in β 0 Rong hib glue is made of machine plastic, and suppressor is a low-end finish. The thinner aluminum or gel plastic under the film is more suitable. The attached layer is used to suck and make it asexual or uniform. The courage is natural, and the solution is to solve the high-grade full-boiled bottle-boiled and cup-boiled 1a. Carbon-coated CB DL 0 vermiculite, rigid.金 出 c (Successful DL technique, thin and thin film η r Γ a (Please read the precautions on the back before filling in this page)
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經濟部中央標準局員工消費合作社印製 ο 度 知硬 周 高 所 , 為碳 具 質 器 晶 驗非 之 間 碳 以 為 膜 之 體 主 為 合 結 滑 光 常 非 而 率 射 折 高 有 具 優 性 緣 絕 驗 實 等 瓶 燒 及 杯 燒 於 用 利 術 技 〇 成 i 形 之 炭 ί 膜 質 C fie TL· ® D 之 該 度將 波 , 面 前 表先 ΰ 膜 塗 之 具 。 器 者 平 開 特 利 專 本 曰 如 載 記 所 報 公 號 平 開 特 Ηϋ ί 專 本 曰 該 裝 成 形 之 膜 C L D 之 載 記 報 公 號 本紙張尺度適用中國國家標準(CNS)A4規格( 210X 297公釐)5修| 493012 A7 B7 五、發明説明(3 ) 置為如下述。即,如圖16所示,具有碳源氣體之導入口 1A 與排氣孔1B之反應室1內配置陰極2,形成在該陰極2之凹 部2A内收容燒杯等之實驗器具3。有接地之陽極4插入於該 實驗器具3之内側之後,從排氣孔1B排氣而減壓反應室1內 之壓力。然後,從導入口 1A導入碳源氣體之後,從高頻電 源5施加高頻電源於陰極3,激勵碳源氣體所發生之等離子 體而在實驗器具3之表面形成DLC膜。 然而,上述之DLC膜之形成裝置,在反應室1內收容陰極 2及陽極4,反應室1之容積,與塗膜對象之實驗器具3之大 小比較起來非常之大,真空操作所費時間多而能源之浪費 多,再者,該DLC膜之形成裝置之形成速度為10〜1000埃/ 分鐘,有其生成速度慢而廉價地連續生產困難之問題存在。 該先前之DLC膜之形成裝置,係Μ燒杯及燒瓶等實驗器 具為對象,對此加上附加價值為目的,因此不考慮製造成 本及製造時間,但啤酒及橘汁等飲料用之填充容器,則需 要大量之廉價品,因此,不能使用該DLC膜形成裝置來製 造飲料用容器。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 又,依上述之DLC膜之形成裝置,碳源氣體會進入陰極2 與塗膜對象之實驗器具3之間的間隙,無法限定在器具3之 內面而實行塗膜。 飲料用之填充容器不同於燒杯或燒瓶,在工廠內之製造 過程中或在販賣途徑中,填充容器互相碰撞或互相摩擦之 機會極多。因此,在飲料用之填充容器外面形成DLC膜時, |lUC膜係薄而硬,因此DLC膜本身會損傷而填充容器之商 品價值。因此,關於飲料用之填充容器,需要只在容器之 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ~~ 經濟部中央標準局員工消費合作社印製 493012 A7 B7 五、發明説明(4 ) 內^面形成D L C膜。 [發明之接要] 本發明係為解決上述先前之問題點所成。即,本發明Θ 的,在於提供可製造在維持塑膠容器之特性的狀態下,消除 塑膠之氣體阻擋性及吸附之問題,使退遷使用為可能以便 擴大塑膠容器之使用形態之同時,可廉價地連鑛生產,而 且在使用處理中不會損傷之碳膜塗膜塑膠容器之製造裝置 及製造方法者。 為達成上述目的,本發明之碳膜塗膜塑膠容器之製造裝 置,具備有為收容容器而形成,設有與所收容容器之外形 呈略相似形之空間之空心狀外部電極,及當容器收容於3 部電極之空間內時,該容器之口部擋接之同時τ絕緣外部電 極之絕緣構件,及被接地而從收专^外部電極之空間内之容 器之口部插入容器內側之內部電極,及連通於外部電極之 空間內而排出空間內氣體之排氣裝置,及對收容於外部電 極之空間內容器之內側供給原料氣體之供給裝置,及連接 於外部電極之高頻電源為其特黴。 再者,本發明之碳膜所塗膜塑膠容器之製造裝置,其內 部電極形係形與收容於外部電極空間内之容器內壁面 形狀略相似形,該內部電極形成有原料氣體之噴出孔,從 供給裝置所供給之原料氣體,係從內部電極之噴出孔噴出 於收容在外部電極空間內之容器內之構成,該內部電極之 噴出孔為形成有一個或複數個,又,在絕緣構件形成有溝 部,收容於外部電極空間内容器之口部擋接於該絕緣構件 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ” (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, known as the Hard Weekly High Institute, which is a carbon device that tests the carbon between the carbon and the film. Exact tests such as bottle-burning and cup-burning are performed with sharp technique 〇 i-shaped charcoal ί film quality C fie TL · ® D will be waved, the front surface is first coated with film. The instrument holder Pingkai Teli special edition is described as published in the publication No. Pingkai special Ηϋ Special edition said that the film formed by the package CLD is published in the publication of the paper The paper size is applicable to China National Standard (CNS) A4 specifications (210X 297 mm) 5 repairs | 493012 A7 B7 5. Description of the invention (3) is set as follows. That is, as shown in Fig. 16, a cathode 2 is arranged in a reaction chamber 1 having an introduction port 1A for carbon source gas and an exhaust hole 1B, and an experimental appliance 3 such as a beaker is housed in a recess 2A of the cathode 2. After the grounded anode 4 is inserted inside the experimental device 3, the anode 4 is exhausted from the exhaust hole 1B and the pressure in the reaction chamber 1 is reduced. After the carbon source gas is introduced from the inlet 1A, a high-frequency power source is applied from the high-frequency power source 5 to the cathode 3, and a plasma generated by the carbon source gas is excited to form a DLC film on the surface of the experimental device 3. However, the above-mentioned DLC film forming device accommodates the cathode 2 and the anode 4 in the reaction chamber 1. The volume of the reaction chamber 1 is very large compared with the size of the experimental equipment 3 of the film coating object, and the vacuum operation takes much time. The waste of energy is large. Furthermore, the formation speed of the DLC film formation device is 10 to 1000 Angstroms / minute, and there is a problem that it is difficult to continuously produce the DLC film at a low speed and at low cost. The previous DLC film forming device was intended for experimental devices such as M beakers and flasks. For the purpose of adding added value, the manufacturing cost and manufacturing time are not considered, but the filling containers for beverages such as beer and orange juice. Since a large number of inexpensive products are required, the DLC film forming apparatus cannot be used to manufacture a container for beverages. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). According to the above-mentioned DLC film forming device, the carbon source gas will enter the cathode 2 and the experimental equipment 3 of the coating object. The gap between them cannot be limited to the inner surface of the device 3 and a coating film can be applied. Filling containers for beverages are different from beakers or flasks. There are many opportunities for filled containers to collide or rub against each other during the manufacturing process in the factory or during the sales route. Therefore, when a DLC film is formed on the outside of a filled container for beverages, the | 1UC film is thin and hard, so the DLC film itself will be damaged and the commercial value of the filled container. Therefore, for filling containers for beverages, only the paper size of the container needs to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) ~~ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 493012 A7 B7 V. Description of the invention (4) A DLC film is formed on the inner surface. [Summary of the Invention] The present invention is made to solve the above-mentioned problems. That is, the invention of Θ is to provide a plastic container that can be manufactured while maintaining the characteristics of the plastic container, eliminating the problems of gas barrier properties and adsorption of the plastic, and making it possible to retreat to expand the use form of the plastic container while being cheap. Manufacturing device and manufacturing method of carbon-coated plastic container produced by Dilian Mine and which will not be damaged during use and processing. In order to achieve the above object, the manufacturing device of the carbon film-coated plastic container of the present invention includes a hollow external electrode formed for accommodating a container, and provided with a space similar to the shape of the container outside, and when the container is accommodated When in the space of 3 electrodes, the mouth of the container is blocked while τ insulating the external electrode insulation member, and the internal electrode that is grounded and inserted from the mouth of the container in the space containing the external electrode into the inside of the container , And an exhaust device that communicates with the space of the external electrode and exhausts the gas in the space, and a supply device that supplies the raw material gas to the inside of the space container housed in the external electrode, and a high-frequency power source connected to the external electrode is special mold. Furthermore, the device for manufacturing a plastic container coated with a carbon film according to the present invention has a shape similar to that of the inner wall surface of the container accommodated in the outer electrode space, and the inner electrode is formed with a raw material gas ejection hole. The raw material gas supplied from the supply device is formed by ejecting from the ejection holes of the internal electrode out of a container housed in the space of the external electrode. The ejection holes of the internal electrode are formed in one or more, and are formed in the insulating member. There is a groove, and the mouth of the inner container contained in the external electrode space is blocked by the insulating member. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) "(Please read the precautions on the back before filling this page)
493012 A7 B7 五、發明説明(5 ) 時,形成在外部電極之內壁面與容器之外壁面之間的空間 ,及容器之內部為由溝部而連通為其特徵。 又,為達成上逑目的,本發明之碳膜所塗莫塑膠容器之 製造方法為,在外部電極形成收容容器而與所收容容器之 外形略相似形之空間,收容於該空間內之容器之口部擋接 之絕緣構件絕緣外部電極,從容器之口部插入内部電極於 收容於空間內之容器之內側的同時,內部電極予K接地, 排出外部電極空間内之氣體,對收容在外部電極空間内之 容器的內側供給原料氣體之後,對外部電極施加高頻為其 特黴。 上述碳膜塗膜塑膠容器之製造裝置及製法,係將塑膠容 器插入於外部電極內而收容。該時,內部電極插入於容器 内。然後,口部擋接於絕緣構件而容器定位於外部電極內 之後,封閉外部電極內。該時,外部電極之内壁面與容器 外壁面之間的間隔為保持為大致上均勻,且容器內壁面與 內部電極外壁面之間的間隔亦保持成為大致上均勻之狀態。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 之後,用排氣裝置排出外部電極內之空氣,使外部電極 內成為真空狀態。該時,藉形成在絕緣構件之溝部,不僅 是排出容器之内部空間的空氣,而容器外壁面與外部電極 之內壁面之間的外部空間亦排氣而成為真空。 之後,從供給裝置供給原料氣體,從形成在内部電極之 噴出孔噴出於真空狀態之內部空間。 供給該原料氣體之後,從高頻電源對外部電極通電。由 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 众_ 493012 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明(6 ) 於該通電,在外部電極與內部電極間發生等離子體。該時 ,内部電極係 接地,但外部電極為由絕緣構件所絕緣, 因此,外部電極發生負的自給偏壓,由此在沿著外部電 極之容器之內壁面均勻地形成碳膜。 根據上逑碳膜所塗膜塑膠容器之製造裝置及製法,由於 製造時間可縮短,且不浪費能源,故可連練生產廉價之碳 膜塗膜塑膠容器。再者,可只限定在容器之内壁面形成碳 膜。 將內部電極形成為內壁面形狀之相似形,藉Μ在容器之 內壁面可均勻地形成碳膜。 由於在内部電極形成有原料氣體之噴出孔,原料氣體為 從容器之中心部均勻地噴出,再者,該噴出孔為形成有一 個或複數個,因此可促進原料氣體之擴散。 再者,由於形成在絕緣構件之溝部,外部電極之内壁面 與容器外壁面之間的空間亦成為真空,可抑制等離子體發 生時之溫度上昇。又,Κ本發明所製造之容器為飲料用瓶 子時,取代先前玻璃容器,可當做可退遷容器使用之。 上述碳膜所塗咚雙膠容器之製法中,容器外壁面與外部電 極內壁面之間的外部空間剛排氣後,立即供給原料氣體於 外部電極之空間內所收容”拿器內側為宜。藉此,容器外部 空間內之壓力為比內部空間內之壓力稍遲開始下降,剛排 氣後外部空間內之壓力比內部空間之壓力稍高,因此,在 剛排氣後立即供給原料氣體,即噴出於内部空間之原料氣 體不會進入外部空間內。 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) (請先閱讀背面之注意事項再填寫本頁) 11 ϋ-ϋ Β^ιϋ mMmmmmtt immTmw il^i - m_i-· nm In·— ·ϋ·ϋ ϋ—^—493012 A7 B7 5. In the description of the invention (5), it is characterized by the space formed between the inner wall surface of the external electrode and the outer wall surface of the container, and the inside of the container is connected by a groove portion. In addition, in order to achieve the above object, the manufacturing method of the plastic film-coated plastic container of the present invention is to form a storage container on the external electrode and have a shape similar to the outside of the stored container, and the container stored in the space. The insulating member connected to the mouth insulates the external electrode. While inserting the internal electrode from the mouth of the container inside the container housed in the space, the internal electrode is grounded to K, and the gas in the external electrode space is exhausted to the external electrode housed. After the raw material gas is supplied to the inside of the container in the space, high frequency is applied to the external electrode to make it special mold. The manufacturing device and manufacturing method of the above-mentioned carbon film-coated plastic container are stored by inserting a plastic container into an external electrode. At this time, the internal electrode is inserted into the container. After that, the mouth is blocked by the insulating member and the container is positioned inside the external electrode, and then the inside of the external electrode is closed. At this time, the interval between the inner wall surface of the external electrode and the outer wall surface of the container is maintained substantially uniform, and the interval between the inner wall surface of the container and the outer wall surface of the internal electrode is maintained substantially uniform. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page), and then exhaust the air inside the external electrodes with a venting device to make the inside of the external electrodes vacuum. At this time, not only the air exhausted from the internal space of the container, but also the external space between the external wall surface of the container and the internal wall surface of the external electrode is evacuated by the groove formed in the insulating member to become a vacuum. Thereafter, the raw material gas is supplied from the supply device, and the internal space in a vacuum state is sprayed from a discharge hole formed in the internal electrode. After the source gas is supplied, an external electrode is energized from a high-frequency power source. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). _ 493012 Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, A7, B7. 5. Description of the invention (6) In this energization, between the external electrode and the internal electrode A plasma occurs. At this time, the internal electrode is grounded, but the external electrode is insulated by an insulating member. Therefore, a negative self-bias voltage is generated on the external electrode, and a carbon film is uniformly formed on the inner wall surface of the container along the external electrode. According to the manufacturing device and manufacturing method of the plastic container coated with the carbon film on the upper side, since the manufacturing time can be shortened and energy is not wasted, it is possible to continuously produce inexpensive carbon film coated plastic containers. Further, the carbon film may be formed only on the inner wall surface of the container. The internal electrode is formed into a shape similar to the shape of the inner wall surface, so that a carbon film can be uniformly formed on the inner wall surface of the container. Since the raw material gas ejection holes are formed in the internal electrode, the raw material gas is uniformly ejected from the center portion of the container. Furthermore, the ejection holes are formed in one or a plurality of holes, thereby promoting the diffusion of the raw material gas. Moreover, since the space between the inner wall surface of the external electrode and the outer wall surface of the container is formed in the groove portion of the insulating member, a temperature rise at the time of plasma generation can be suppressed. When the container produced by the present invention is a beverage bottle, it can be used as a recyclable container instead of the previous glass container. In the above-mentioned method for manufacturing a double-glue container coated with carbon film, it is preferable that immediately after the external space between the outer wall surface of the container and the inner wall surface of the external electrode is exhausted, a raw material gas is supplied to the space of the external electrode to be accommodated. As a result, the pressure in the outer space of the container starts to drop slightly later than the pressure in the inner space. The pressure in the outer space immediately after the exhaust is slightly higher than the pressure in the inner space. Therefore, the raw material gas is supplied immediately after the exhaust. That is, the raw material gas sprayed from the inner space will not enter the outer space. This paper size applies the Chinese National Standard (CNS) Α4 size (210X297 mm) (Please read the precautions on the back before filling this page) 11 ϋ-ϋ Β ^ ιϋ mMmmmmtt immTmw il ^ i-m_i- · nm In · — · ϋ · ϋ ϋ — ^ —
W1T 493012 85. A7 B7 五、發明説明(7 體化 氣性 機活 無面 M壁 應内 , 之 前 器 Μ 容 膜使 塗可 膜 , 碳此 行藉 進 ο 器宜 容為 膠理 塑處 對體 在子 , 離 者等 Hy 一丁 ^Hr /f 實 一 可 2 且 1 > 10間 為 時 定氣 設排 應 之 度化 ο 空空 性真真 接之短 密氣縮 之排可 膝内, 塑間此 與空如 膜極 。 塗電佳 膜 部 為 碳外ΓΓ 高,to 提者 5 可 再 - 量 匕匕 爾 之 需 Fr tK ί 省 節 裝 造 製 之 用 器 容 膠 塑 膜 塗 所 膜 碳 明 發 J 本 明造 說製 單 不 簡顯 之 為 式gl i圖 的 例 施 實 置 圖 圖 面 剖 之 示 顯 而 大 放 Μ 予 分 fy 0 之 例 施 質 該 為 2 圖 側 的 例 施 實 〇 之 圖't? 面容 平膠 之塑 板膜 熱塗 隔 所 之 膜 例 碳 施明 實 發 該本 示一不 顯顯 為 為 3 4 _11 評 的 等 厚 膜 之 膜 碳 質 硬 之 成 形 所 件 條 i - 之 碳5 質 圖 硬依 示 示 。 顯顯 圖 5 6 面圖圖 lir 表 件 條 成 形 之 (請先閲讀背面之注意事項再填寫本頁) '訂W1T 493012 85. A7 B7 V. Description of the invention (7 Body gasification machine with no surface M wall should be inside, the front device M container film can be coated with film, and the carbon borrowed here. The device should be filled with plastic and plastic. Being in the body, leaving the person, etc. Hy H ^ Hr / f 一 可 2 and 1 > 10 time constant gas set the degree of exhaustion ο the air is really close to the short dense air contraction can be in the knee The plastic room is as empty as a membrane pole. The coated electric film is high in carbon and ΓΓ, and it can be lifted to 5 times-the amount of the required amount is Fr tK. The film carbon Mingfa J Benming said that the manufacturing order is not a simple example of the formula gl i, the implementation of the drawing is shown in the figure, and the magnification M is divided into fy 0. The example of the example of the implementation of the picture 't? The face of the plastic film of the plastic film thermal coating compartment example of carbon Shi Mingshi issued this display is not significantly marked as 3 4 _11 film of the same thickness of the film is hard Forming the strip i-the carbon 5 quality picture is shown in hard. Show the figure 5 6 side view picture lir table piece Formed (Please read the notes on the back before filling this page)
表 果 結圖 fi--lp 顯 為 之 5 圓 依 一5 等 度 過 透、 氧 之 膜 碳 質 硬 之 成 形 所 經濟部中央標準局員工消費合作社印製 紫 之 器 容 膠 塑 之 膜 碳 質 硬 有 成 杉 J/ 條 之 5 圖 ο 6 表TMr: ϊ為 8 評圖 視 可 外The results show that fi--lp is 5 rounds, and the 5th grade is a transparent, oxygen film. The carbon film is hard. The Ministry of Economic Affairs, Central Standards Bureau, Employees Cooperative Co., Ltd. printed purple container plastic film. Hardly made cedar J / Article 5 Figure ο 6 Table TMr: ϊ is 8 Comments can be viewed outside
II 譜 光 曼 拉 之 膜 碳 質 硬 ο 之 表成 _ 形 的所 譜件 光條 過 之 iil15 之 内 域 依 二卜 Μ δ 為 的 等 厚 膜 之 膜 。 碳 表質 件硬 條 之 成成 形 形 他所 其件 之 條 膜之 碳10 質圖 硬 依 示一不 顯顯 為為 Λυ ϋ oil 表圖圖 圖 木紙張您度適/0中阀同家標卒(CNS ) Λ4規格(210X297公雄)1 〇.條jp ▼ 493012 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明(8 ) 評估結果表。 圖12為顯示依圖10之條件所形成之硬質碳膜之氧透過度 等的評估結果表。 圖13為顯示硬質碳膜之再其他形成條件表。 圖14為顯示依圖13之條件所形成之硬質碳膜之膜厚等的 評估結果表。 圖15為顯示依圖13之條件所形成之硬質碳膜之氧透過度 等的評估結果表。 圖16為顯示先前技術之剖面圖。 [發明之詳细描述] 玆根據圖式說明本發明之實施例如下。 圖1為顯示製造本發明碳膜所塗膜塑膠容器之製造裝置 。該製造裝置,在基台10上安裝陶磁製之絕緣板11,該絕 緣板11上安裝外部電極12。該外部電極12,兼作DLC膜形 成用之真空室,其內部形成有收容塗膜對象之容器20用的 空間。該外部電極12內之空間係形成為稍大於收容在該空 間之容器20的外形。該容器20為飲料用瓶子,但其他用途 之容器亦可。 外部電極1 2,係由本體部1 2 A,及裝卸自如地安裝在該 本體部12A上部而密封本體部12A內部之蓋體12B所構成。 藉整合器13而有高頻電源14連接於該外部電極12。又,在 外部電極12內之空間內有連通排氣管15,藉未圖示之真空 泵排出空間內之空氣。有內部電極16插入於外部電極12之 空間內,配置成為位於空間之中心部。該内部電極1 6係成為 (請先閲讀背面之注意事The film of the II spectrum light Manla is carbonaceous. The thickness of the inner region of the iil15 that passes through the light bar is equal to the thickness of the film. The carbon surface of the hard strips is shaped into the shape of the strips of other pieces of carbon. The 10 quality maps are hard to show, and are not obvious as Λυ ϋ oil. (CNS) Λ4 specification (210X297 male) 1 0.0. Jp ▼ 493012 A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (8) Evaluation result table. Fig. 12 is a table showing evaluation results of oxygen permeability and the like of the hard carbon film formed under the conditions shown in Fig. 10. FIG. 13 is a table showing still other conditions for forming a hard carbon film. Fig. 14 is a table showing evaluation results of the film thickness and the like of the hard carbon film formed under the conditions shown in Fig. 13. Fig. 15 is a table showing evaluation results of oxygen permeability and the like of the hard carbon film formed under the conditions shown in Fig. 13. Fig. 16 is a sectional view showing a prior art. [Detailed Description of the Invention] An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 shows a manufacturing apparatus for manufacturing a plastic container coated with a carbon film of the present invention. In this manufacturing apparatus, a ceramic magnetic insulating plate 11 is mounted on a base 10, and an external electrode 12 is mounted on the insulating plate 11. The external electrode 12 also serves as a vacuum chamber for forming a DLC film, and a space for a container 20 for receiving a coating film object is formed inside the external chamber. The space inside the external electrode 12 is formed slightly larger than the outer shape of the container 20 housed in the space. The container 20 is a bottle for beverages, but other containers may be used. The external electrode 12 is composed of a main body portion 12 A and a cover 12B which is detachably mounted on the upper portion of the main body portion 12A and seals the inside of the main body portion 12A. A high-frequency power source 14 is connected to the external electrode 12 via the integrator 13. Further, the space inside the external electrode 12 is provided with a communication exhaust pipe 15, and the air in the space is exhausted by a vacuum pump (not shown). The internal electrode 16 is inserted into the space of the external electrode 12, and is arranged so as to be located at the center of the space. The internal electrodes 1 to 6 become (Please read the notes on the back first
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本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 493012This paper size applies to China National Standard (CNS) A4 (210X297 mm) 493012
經濟部中央標準局员工消费合作社印製 五、發明説明(9 ) 可從容器2 0之口部2 0 A插入於容器内且其外形與容器2 0之 内部形狀呈駱相似形。外部電極1 2與内部電極1 6之間隔,Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (9) The mouth 20A of the container 20 can be inserted into the container and its shape is similar to the internal shape of the container 20. The distance between the external electrode 12 and the internal electrode 16
I 在任何位置,在1 0〜1 5 0 in m之範圍内,保持成為均勻為宜。 有原料氣體供給管1 7連接於該內部電極1 6,藉未圖示之 氣體流量控制器,有原料氣體流入該原料氣體供給管1 7, 從形成在內部電極1 6之噴出孔1 6 A噴出之構成。 為了能使 所噴出之原料氣體均勻地擴散,在内部電極1 6之側部形成 複數個該噴岀孔1 6 如圖所示為宜,但若原科氣體立即可 均勻擴散時,在內§卩電極1 6之頂部形成一個亦可。内部電 極16為藉原料氣體供給管17而接地。 絕緣板11上,如在圖2及圖3所放大而顯示,形成有複數 個(在本實施例中即四個)之溝部Η A,從圖2可了解,收容 容器2 0於外部電極1 2内容器2 0之口部2 0 A擋接於絕緣板1 1 之狀態下,形成在外部電極12之內壁面與容器20外壁面之 間的容器之外部空間2 1 A與排氣管1 5為藉溝11 A而達通之構 成。 其次,將用上逑製造裝置形咸D L C膜之方法說明如下。 外部電極12內,卸下蓋體12B之狀態下,從本體部12A之 上部開口部插入塑膠製之容器20而收容之。該時,内部電 極1 6為從容器2 0之口部2 0 A插入於容器2 q內。然後,口部 2 0 A擋接於絕緣板1 1上,容器2 0在外部電極1 2内定位之後 ,關上篕體1 2 B,以密封外部電極1 2内部。該時,外部電 極1 2之内壁面與容器2 0外壁面之間的間隔係保持為略均勻 ,且容器2 0之内壁面與内部電極1 6之外壁面之間的間隔亦 本紙張尺度適;fl中國國家標率((’NS ) Λ4規格(210X 297公釐) _ ίο _ JtjL. χ (請先閲讀背面之注意事項再填寫本頁) 訂 Μ 493012 經濟部中央橾準局員工消費合作社印製 Α7 Β7五、發明説明(1 Ο ) 保持成為略均匀。 之後,用真空泵排出外部電極1 2内之空氣,使外部電極 1 2内成為真空。該時,藉形成在絕緣板1 1之溝部1 1 A,不 僅是排出容器2 0之内部空間2 1 B,同時排出容器2 0之外壁 面與外部電極1 2内壁面之間的外部空間2 1 A之空氣而成真 空狀態。此乃若外部空間2 1 Λ非真空時,在後述要發生等 離子體之際,該外部空間2 1 /\内變為高溫,對容器2 0之塑 膠材質有不良影響之關ί系。 該時之真空度為以1 0 — 2〜1 0 — 5 t 〇 r r為宜。其原因為 ,10 - 1 Μ上之真空度時容器内之不純物過多,未滿 1 0 — 5之真空度時,排氣時需要過多時間及能量之關係。 之後,從未圖示之氣體流量控制器對原料氣體烘給管1 7 供給碳源之原料氣體,從形成在內部電極1 6之噴出孔1 6 Λ 噴出於真空狀態之内部空間2 1 Β内。該原料氣體Κ 1〜1 〇 〇 m 1 / m ί η之量烘給為宜,由於該原料氣體之供給而調整内部 空間2 1 Β内之壓力為0 . 5〜0 . 0 1 t 〇 r r之範圍内。 外部空間2 1 Λ内係藉溝部1 1 A而排氣,因此,外部空間2 1 A 内之壓力為較内部空間2 1 B内之壓力稍遲而降低。因此, 剛排氣之後外部空間2 1 Λ內之壓力稍為高於内部空間2 1 B。 因此,剛排氣之後立即供給原料氣體,即噴出於内部空間 2 1 Β内之原料氣體不會進入外部空間2 1 Λ内。 使用室溫下圼氣體或液體之脂肪族碳化氫類,芳香族碳化 氫類,含氧碳化氫類,含氮碳化氫類等做為原料氣體。尤其是 (請先閱讀背面之注意事項再填寫本頁) 裝· 、1Τ 木紙尕尺度適巾阀阀家標冬(CNS ) Λ4規格U10X297公f ) ! 3修正夏 經濟部中央標準局員工消費合作社印製 493012 A7 B7 五、發明説明(u) 碳數量為6K上之苯,甲苯,〇 -二甲苯,m -二甲苯,p-二 甲苯,環己烷等為宜。該原料為可單獨使用,或M2種以 上之混合氣體而使用。再者,該等氣體用氩或氦等稀有氣 體稀釋使用亦可。 供給該原料氣體之後,從高頻電源14藉整合器13而對外 部電極12通電。由於該通電而在外部電極12與内部電極16 間發生等離子體。該時,内部電極16為接地,但外部電極 12為由絕緣板11所絕緣,因此,外部電極12發生負之自給 偏壓,因此在沿著外部電極12之容器20之內壁面均勻地形 成DLC膜。 即,容器20內壁面之DLC膜之形成,係由蚊良之等離子體 CVD法所實行。依該等雛子體CVD法,利用低溫等離子體, 而可將DLC膜形成時之溫度設定為較低溫度,因此,適合 於Μ塑膠等耐熱性不良物品做基盤時之處理,而且可以較 廉價而形成較廣大面積之DLC膜。 在此所諝低溫等離子體者,係指反應器內部維持成為低 壓時,等離子體中之電子溫度為高,而雛子及中性分子之 溫度為比該溫度顯著地低之狀態的等離子體,即,所諝非 平衡狀態之等雛子體而言。 在外部電極12與內部電極16之間發生等離子體時,被絕 緣之外部電極12之内壁面積存電子而該外部電極12為自給 偏壓成為負電位。由於該積存電子,在外部電極12側產生 500〜1000V左右之電位下降。該時,在等雛子體中有存在 成為碳源之碳酸氣體,因此*離子化#為正之碳源為撰擇 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) 一 - (請先閲讀背面之注意事項再填寫本頁)It is advisable to keep it uniform at any position within the range of 10 to 150 in m. A raw material gas supply pipe 17 is connected to the internal electrode 16. By means of a gas flow controller (not shown), a raw material gas flows into the raw gas supply pipe 17 from an ejection hole 16 A formed in the internal electrode 16. Squirting composition. In order to make the ejected raw material gas uniformly diffuse, it is appropriate to form a plurality of the nozzle holes 16 on the side of the internal electrode 16 as shown in the figure, but if the original gas can be uniformly diffused immediately, the internal § 卩One electrode may be formed on the top of the electrode 16. The internal electrode 16 is grounded via a source gas supply pipe 17. As shown in FIG. 2 and FIG. 3, the insulation plate 11 is enlarged and formed with a plurality of groove portions Η A (four in this embodiment). As can be understood from FIG. 2, the storage container 20 is located on the external electrode 1. 2 Inner container 2 0 mouth 2 0 A is blocked on the insulating plate 1 1, and the outer space 2 1 A of the container and the exhaust pipe 1 are formed between the inner wall surface of the external electrode 12 and the outer wall surface of the container 20 5 is constituted by a trench 11 A. Next, a method for manufacturing a device-shaped salty D L C film by using the upper part will be described as follows. In the external electrode 12, with the lid 12B removed, a plastic container 20 is inserted from the upper opening of the main body portion 12A to be accommodated therein. At this time, the internal electrode 16 is inserted into the container 2 q from the mouth portion 20 A of the container 20. Then, the mouth portion 20 A is blocked on the insulating plate 11. After the container 20 is positioned in the external electrode 12, the carcass 1 2 B is closed to seal the inside of the external electrode 12. At this time, the interval between the inner wall surface of the external electrode 12 and the outer wall surface of the container 20 is kept slightly uniform, and the interval between the inner wall surface of the container 20 and the outer wall surface of the internal electrode 16 is also suitable for this paper. ; fl China National Standard (('NS) Λ4 Specification (210X 297mm) _ ίο _ JtjL. χ (Please read the notes on the back before filling out this page) Order M 493012 Staff Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Printed A7, B7, V. Description of the invention (1 0) remains slightly uniform. After that, the air inside the external electrode 12 is exhausted by a vacuum pump to make the inside of the external electrode 12 vacuum. At this time, it is formed on the insulating plate 1 1 The groove portion 1 1 A is not only exhausted from the internal space 2 1 B of the container 20 but also exhausted from the external space 2 1 A between the outer wall surface of the container 20 and the inner wall surface of the external electrode 12 to form a vacuum state. This is If the external space 2 1 Λ is not a vacuum, when the plasma to be described later occurs, the external space 2 1 / \ becomes high temperature, which has a negative impact on the plastic material of the container 20. The vacuum at this time The degree is preferably 1 0 — 2 to 1 0 — 5 t 〇rr The reason is that there is too much impurities in the container at the vacuum degree of 10-1 Μ, and when the vacuum degree is less than 10-5, the relationship between excessive time and energy is required for exhaust. After that, the gas flow rate is not shown. The controller bakes the raw material gas to the raw material gas supply tube 17 and supplies the raw material gas of the carbon source from the ejection holes 16 formed in the internal electrode 16 to the internal space 2 1 Β which is in a vacuum state. The raw material gas K 1 to 1 〇 〇m 1 / m ί η is suitable for baking, the internal space 2 1 Β is adjusted due to the supply of the raw material gas pressure within the range of 0.5 ~ 0. 0 1 t 〇rr. External space 2 1 Λ is exhausted by the groove 1 1 A. Therefore, the pressure in the outer space 2 1 A is slightly lower than the pressure in the inner space 2 1 B. Therefore, immediately after the exhaust, the outer space 2 1 Λ The pressure is slightly higher than the internal space 2 1 B. Therefore, the raw material gas is supplied immediately after venting, that is, the raw material gas sprayed out of the internal space 2 1 Β will not enter the external space 2 1 Λ. Use room temperature krypton gas or Liquid aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated carbons Type, nitrogen-containing hydrocarbons, etc. as the raw material gas. Especially (please read the precautions on the back before filling in this page). · 1T wood paper and paper size standard towel valve valve standard winter (CNS) Λ4 specification U10X297 male f)! 3 Amendment printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, 493012 A7 B7 V. Description of the invention (u) Benzene, toluene, 0-xylene, m-xylene, p-xylene with a carbon content of 6K Cyclohexane is suitable. This raw material can be used alone or as a mixture of two or more kinds of gases. Furthermore, these gases may be diluted with a rare gas such as argon or helium for use. After the raw material gas is supplied, the external electrode 12 is energized from the high-frequency power source 14 via the adapter 13. Due to this energization, plasma is generated between the external electrode 12 and the internal electrode 16. At this time, the internal electrode 16 is grounded, but the external electrode 12 is insulated by the insulating plate 11. Therefore, a negative self-bias voltage is generated on the external electrode 12, so that DLC is uniformly formed on the inner wall surface of the container 20 along the external electrode 12. membrane. That is, the formation of the DLC film on the inner wall surface of the container 20 is performed by the mosquito plasma CVD method. According to these young daughter CVD methods, the temperature at the time of DLC film formation can be set to a lower temperature by using low-temperature plasma. Therefore, it is suitable for the processing of poorly heat-resistant articles such as M plastics as substrates, and can be cheaper and cheaper. A larger area of DLC film is formed. The term "low-temperature plasma" refers to a plasma in which the temperature of electrons in the plasma is high while the temperature of the chicks and neutral molecules is significantly lower than the temperature when the reactor is maintained at a low pressure, that is, , In terms of the unbalanced state of the young daughter body. When a plasma is generated between the external electrode 12 and the internal electrode 16, electrons are stored in the inner wall area of the insulated external electrode 12, and the external electrode 12 becomes self-biased to a negative potential. Due to the accumulated electrons, a potential drop of about 500 to 1000 V occurs on the external electrode 12 side. At this time, there is a carbonic acid gas that is a carbon source in the embryo body. Therefore, * Ionization # is positive. The carbon source is selected. This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm). (Read the notes on the back before filling out this page)
493012 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明(1 2) 性碰撞於沿著外部電極1 2之容器2 0之内壁面,接著,接近 之碳為互相結合,在容器2 0之内壁面形成極細緻之D L C膜 所成之硬質碳膜。 再者,所謂由DLC膜所成之硬質碳膜係又稱為i碳膜或氫 化非晶質碳膜U - C : II)之硬質碳膜,M S P 3結合為主體之 非晶質碳膜。 DLC膜之膜厚係依高頻之輸出,容器20内之原料氣體之 壓力,供給氣體流量,等離子體發生時間,自給偏壓,及 原料之種類等而定,但為了求低分子有機化合物之吸著抑 制效果及氣體阻擋性之提昇效果,及與塑之密接性,耐久 性及透明性等之兩立,Κ0.05〜5/im為宜。 又,DLC膜之膜質亦同樣依高頻之輸出,容器20内之原 料氣體的壓力,供紿氣體流量,等離子體發生時間,自給 Μ壓,及原料之種類等而定。高頻輸出之增加,容器2 0内 原料氣體之壓力減少,供給氣體流量減少,自給偏壓之增 加,及原料之碳數降低等,均成為DLC膜之硬化,细緻度 之提高,壓縮應力之增大及脆弱增加之原因。因此,維持 與塑膠之密接性及膜之耐久性的同時要最大限度發揮低分 子有機化合物之吸著抑制效果及氣體阻擋效果,即設定成 為高頻輸出為5 0〜1 0 0 0 W ,容器2 0内之原料氣體壓力為0 · 2 0 〜0 , 0 1 t 〇 r r,供給氣之流量為1 0〜5 0 m 1 / m i η,自給偏壓為 -2 0 0〜-1 0 0 0 V,原料氣體之碳數量為1〜8個左右為佳ϋ 再著,為更提DLC高膜與塑膠之密接性,在形成DLC膜之 前,用氬或氧等無機氣體實行等離子處理,使容器2 0之内 本紙張尺度適用中國國家標準(CN、S ) Λ4規格(21〇X 297公釐)1 5修正頁 (請先閱讀背面之注意事項再填寫本頁) 493012 經濟部中央標準局員工消費合作社印製 A7 B7 ____ 五、發明説明(13 ) 壁活性化亦可。 圖4為顯示Μ上述方法形成有DLC膜之塑膠容器之側剖面 。圖中,20A為塑膠材料,20B為形成在塑膠材料20A内壁 面之DLC膜。如此用DLC膜20B塗膜內壁面之塑膠容器’不 僅可顯著地減少氧及二氧化碳等低分子無機令體之透過度 ,而且可完全抑制具有氣味之各種低分子有機化合物K著 。又,因該DLC膜之形成而損 塑膠容器原有之透明性。 再者,形成容器20之塑膠材料’有如聚L烯樹脂’聚丙 烯樹脂,聚笨乙烯,環烯烴共聚體樹脂’聚對苯二甲酸乙 二醇酯樹脂,聚烯荼酯樹脂,乙烯—乙烯醇共聚體樹脂, 聚-4-甲基戊烷-1樹脂,聚甲基丙烯酸甲_樹酯,丙烯腈 樹脂,聚氯乙烯樹脂,聚偏二氯乙烯樹脂,丙烯腈苯乙烯 樹脂,丙烯腈‘ 丁二炔·笨乙烯樹脂,聚醯胺樹脂,聚醯 胺醯亞昀樹脂,聚縮醛樹脂,聚碳酸酯樹脂,聚丁烯對苯二 酸酯,離子鐽聚合樹脂,聚磺樹脂*及4-氟化乙烯樹脂等。 就上述製造裝置及製法所製造之碳膜所塗膜塑膠容器所 實行之(l)DLC膜之膜厚,(2)DLC膜之密度,(3)密接性1, (4)密接性2,(5)耐鹼性,(6)碳酸氣阻擋性,(7)氧氣阻 擋性,(8)低分子有機化合物(香料成份)之吸著性的各評 估結果為如下述。又,各評估方法係按下紡4爲之。 (1) DLC膜之膜厚 預先在容器之内面用萬能墨水等實行遮蔽,覆蓋DLC之 後,用二乙醚等徐去該遮蔽,用別克(VECC0)公司製造之 表面形狀測定器狄克達克3(DECTACK 3)測定膜厚。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 16 (請先閱讀背面之注意事項再填寫本頁)493012 Printed by A7 B7, Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the Invention (1 2) It collided with the inner wall surface of the container 2 0 along the external electrode 12. Then, the approaching carbon was combined with each other. The inner wall surface of 0 forms a hard carbon film formed by an extremely fine DLC film. In addition, the so-called hard carbon film formed of a DLC film is also referred to as an i-carbon film or a hydrogenated amorphous carbon film (U-C: II), and M S P 3 is an amorphous carbon film combined as a main body. The thickness of the DLC film is determined by the output of high frequency, the pressure of the raw material gas in the container 20, the supply gas flow rate, the plasma generation time, the self-bias voltage, and the type of the raw material. The absorption inhibition effect and the improvement effect of the gas barrier property, and the adhesiveness with plastic, durability and transparency, etc., are preferably K0.05 ~ 5 / im. In addition, the film quality of the DLC film also depends on the high-frequency output, the pressure of the raw material gas in the container 20, the flow rate of the tritium gas, the plasma generation time, the self-supplying pressure, and the type of raw material. The increase in high-frequency output reduces the pressure of the raw material gas in the container 20, reduces the supply gas flow rate, increases the self-supply bias voltage, and reduces the carbon number of the raw material. All of these have become the hardening of the DLC film, increasing the fineness and compressive stress. Causes of increased and increased vulnerability. Therefore, to maintain the adhesion to plastic and the durability of the film, it is necessary to maximize the absorption suppression effect and gas barrier effect of low molecular organic compounds, that is, set the high frequency output to 50 ~ 100 00 W, the container The pressure of the raw material gas in 2 0 is 0 · 2 0 ~ 0, 0 1 t 〇rr, the flow rate of the supply gas is 1 0 ~ 5 0 m 1 / mi η, and the self-bias voltage is -2 0 0 ~ -1 0 0 0 V, the amount of carbon in the raw material gas is preferably about 1 to 8. Then, in order to improve the adhesion between the DLC film and the plastic, before forming the DLC film, perform plasma treatment with an inorganic gas such as argon or oxygen to make Containers within 20 This paper size applies to Chinese national standards (CN, S) Λ4 specifications (21 × 297 mm) 1 5 correction page (please read the precautions on the back before filling this page) 493012 Central Bureau of Standards, Ministry of Economic Affairs Printed by employee consumer cooperative A7 B7 ____ V. Description of invention (13) Wall activation is also possible. FIG. 4 is a side sectional view showing a plastic container having a DLC film formed by the above-mentioned method. In the figure, 20A is a plastic material, and 20B is a DLC film formed on the inner wall surface of the plastic material 20A. Thus, using the DLC film 20B to coat the inner wall of the plastic container 'not only significantly reduces the permeability of low molecular inorganic inorganic substances such as oxygen and carbon dioxide, but also completely suppresses various low molecular organic compounds with odor. In addition, the original transparency of the plastic container is impaired due to the formation of the DLC film. Furthermore, the plastic materials forming the container 20 are, for example, polypropylene resin, polypropylene resin, polyethylene, cycloolefin copolymer resin, polyethylene terephthalate resin, polyolefin resin, and ethylene-ethylene. Alcohol copolymer resin, poly-4-methylpentane-1 resin, polymethyl methacrylate, acrylonitrile resin, polyvinyl chloride resin, polyvinylidene chloride resin, acrylonitrile styrene resin, acrylonitrile '' Butadiyne · Styrene resin, Polyamide resin, Polyamide resin, Polyacetal resin, Polycarbonate resin, Polybutylene terephthalate, Ion resin, Polysulfone resin * And 4-fluorinated ethylene resin. Regarding the plastic container coated with carbon film produced by the above manufacturing apparatus and manufacturing method, (l) the thickness of the DLC film, (2) the density of the DLC film, (3) the adhesiveness 1, (4) the adhesiveness 2, (5) Alkali resistance, (6) Carbon dioxide gas barrier properties, (7) Oxygen barrier properties, (8) Adsorption properties of low molecular organic compounds (fragrance components) are as follows. In addition, each evaluation method is performed by spinning down. (1) The thickness of the DLC film is masked with universal ink or the like on the inner surface of the container in advance. After covering the DLC, the mask is removed with diethyl ether, etc., and the surface shape measuring device Dickard 3 manufactured by Bucc (VECC0) is used. (DECTACK 3) The film thickness was measured. This paper size applies to China National Standard (CNS) A4 (210X297 mm) 16 (Please read the precautions on the back before filling this page)
經濟部中央標準局員工消費合作社印製 493012 A7 _B7__ 五、發明説明(14 ) (2 ) D L C膜之密度 測定成膜前膜後之重量差,從(1)所求得之膜厚算出 密度。 (3)密接性1 按照JlSk 5400之方格子帶子法之規定,以上述條件對容 器之側壁部實行之。 1 ·切痕之間隔:1mm 2·方格子之數量:100 (4 )密接性2 用新東科學公司製造之連續加重式刮傷試驗機黑頓22 (HEID0N 22),以下逑條件,對容器之側壁部實行。密接 之程度,係K加在膜開始剝離時之刮傷針的垂直加重表示 之0 1 .刮傷針之材料,形狀·•鑽石,5 0 a R。 2, 加重速度:100g/min 3. 台架速度:1000mm/min (5)耐鹸性 添加氫氧化納而成為10重之鹼性溶液填充於容器内 部,浸潰於75 °C之熱水中24小時,觀察DLC之形狀變化’ 有友剝離。結果,經24小時Μ上之浸瀆後無變化者為優, 經12小時Κ上之浸漬後無變化者為良而表示之。 (6 )碳酸氣阻擋性 使用摩登控制社(MODERN CONTROL)製造之巴馬杜籣型 (PERMATRANC-4),在25°C1:測定碳酸氣體之透過量。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐). _ 17 - (請先閲讀背面之注意事項再填寫本頁)Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 493012 A7 _B7__ V. Description of the Invention (14) (2) D L C Film Density Determine the weight difference after film formation, and calculate the density from the film thickness obtained in (1). (3) Adhesiveness 1 According to the J1Sk 5400 square grid tape method, the above conditions are applied to the side wall of the container. 1. The interval between cuts: 1mm 2. The number of square grids: 100 (4) Adhesiveness 2 The continuous weighted scratch tester Heidon 22 (HEID0N 22) manufactured by Xindong Science Co., Ltd. is used for the container under the following conditions The side wall portion is implemented. The degree of close contact is K 1 plus the vertical weight of the scratched needle at the beginning of film peeling. 0 1. The material of the scratched needle, shape, diamond, 50 a R. 2. Weighting speed: 100g / min 3. Bench speed: 1000mm / min (5) Ruggedness resistance Sodium hydroxide is added to make a 10-weight alkaline solution into the container and immersed in hot water at 75 ° C 24 hours, observe the shape change of DLC 'youyou peel. As a result, those who had no change after 24 hours of immersion on M were superior, and those who had no change after 12 hours of immersion on K were good. (6) Carbon dioxide gas barrier properties A PERMATRANC-4 manufactured by MODERN CONTROL was used at 25 ° C1 to measure the carbon dioxide gas permeability. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm). _ 17-(Please read the precautions on the back before filling this page)
-,1T 493012 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(15 ) (7 )氧氣阻擋性 使用摩登控制社(MODERN CONTROL)製造之歐克斯-杜籣 杜英(八m /L· :),在40 1C下測定氧之透過量。 (8)低分子有機化合物(香料成份)ϋϋ 使用具有氣味之低分子有機化合物(香料成份)做為環境 材料之一種,Κ松并等之方法(J. Ajic.Food.Chem. 1992, 40, 1902-1905)為參考而實行實驗。 順序為如下述。 1. 備製分別添加各種香料成份(η-辛烷,η-辛醛,η-辛 醇,己”酸乙基,d -檸檬烯)各1 0 0 ρ P m之0 · 3糖醚溶液,做 為試驗樣品香料溶液。 2. 將試驗樣品香料溶液700ml填充於容器內,加蓋之後 ,在20 °C下保存一個月。 3 . —個月後,廢棄試驗樣品香料溶液,用6 0 °C之蒸餾水 洗淨容器內部之後乾燥。 4. 填充二乙醚,抽出吸著於容器之香料成份。 5. 從容器內取出二乙醚,添加硫酸鈉酐而使其脫水之。 6. 戊烷基苯為內標準,用氣相色譜儀實行定量分析。结 果,在容器中有lppm之香料成份存在之水溶液時表 示吸著於容器之香料成份。因此,單位為wg/F>pm/|)〇ttle。 [試驗 1] 將容量700ml之聚對苯二甲酸乙二醇酯樹脂製容器(三井 PET樹脂公司製PET樹脂,型式L125)做為塑膠容器而收容 於圖1之外部電極12內而固定之。 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -,ιτ 經濟部中央標準局員工消費合作杜印製 493012 A7 B7 五、發明説明(1 6) 其次,開動真空泵,外部電極1 2内成為1 0 _ 4 t 〇 r r K下 之真空(背壓)之後,K 3 0 m 1 . m i ri之流速導入氬於塑膠容器 内,使壓力成為0 . 0 4 t 〇 r r做為前處理,通Μ 3 0 0 W之R f電力 Μ等離子體處理容器內面。之後,使用氬做為輔助氣體, 導入Φ苯,環己烷,苯式Ρ -二甲苯,苯或Ρ -二甲苯於容器 内做為原料氣體,Κ圖5所示條件,在容器内面均勻地塗 覆 D L C。 [試驗結果] 膜厚,成膜速度,密度,密接性1,密接性2,耐鹼性之 各評估結果為如圖6所示。密度均為超過2 . 0 0 g / c m 3 ,膜 (系極為細緻。 方格子試驗之結果,可明白與聚乙烯對苯二酸酯樹脂之 密接性為良好,可充分耐實際使用。又,耐鹼性亦無間題 ,D L C之膜極為穩定,可了解完全地保護聚乙烯對二酸酯 樹脂。 關於氧透過度,二氧化碳透過度及各種香料成份之吸著 之程度的結果為如圖7所示。細緻之D L C膜不僅是可完全抑 制香料成份之吸著,且有效抑制二氣化碳之透過。 又,在圖8中顯示内面塗S D L C膜之塑膠容器軀幹部之紫 外可視光領域内之透過光譜。 從約5 0 0 n m前後到紫外部之範圍,透過率急遽減少,表 示D L C膜之塗膜可有效抑製内容物因受到紫外線之劣化。 圖9,Μ試驗1之條件塗覆在塑膠容器軀幹部之薄膜之拉 曼光譜。 本纸張尺度適用中國國家標準(CNS ) Λ4規格(210X297公釐)1 9修罗 ▼裝-- (請先閱讀背面之注意事項再填寫本頁) 訂 Φ 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 493012 A7 B7 五、發明説明(17 ) [試驗 2 ] 除了使用容^ 700 ml之聚丙烯♦苯乙烯共聚合物樹脂製 容器(二菱孟山多化成公司製品:PAN樹脂,型號 L700)做為塑膠容器K外,其餘為如同試驗1之方法在容器 內面形成DLC膜。形成DLC膜之條件為如圖10所示。又,如 同試驗1之方法,就膜厚,密度,密接性1,密接性2,耐 鹼性,碳酸氣阻擋性,氧氣阻擋性,及低分子有機化合物 之吸著性分別實行試驗。 [試驗結果] 關於膜厚,密度,密接性1,密接性2,耐鹼性之試驗結 果為如圖11所示。關於膜厚及密度為如1¾式驗1,情形良好 。又,關於密接性1及密接性2為如因試驗1無任何問題, DLC與聚丙烯♦苯乙烯共聚合物樹脂之密接性為如同聚對 苯二甲酸乙二醇酯樹脂,實用上並無問題。 透過度,二氧化碳透過度各種香料成分之吸著之程 度之結果為如圖12所示。即,聚丙烯♦苯乙烯共聚合物樹 脂之氣體阻擋性本來就優良,再者,經塗覆DLC之後,明 白了氧及二氧化碳之透過量為到達極低之水準。各種香料 成份之吸著量,如同試驗1,在測出界限K下,在感官評 估中亦無問題。 [試驗 3 ] 除了使用容量700ml之環烯烴共聚合物樹脂製容器(三井 石油化學公司製品:C0C樹脂型號APL6015)做為塑膠容器 以外,其餘為如同試驗1之方法在容器内面形成DLC膜。形 -20 - (請先閱讀背面之注意事項再填寫本頁)-, 1T 493012 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (15) (7) Oxygen-barrier use of OX-DU DU DU YING (MODEL CONTROL) manufactured by MODERN CONTROL (eight m / L · :), the oxygen permeation amount was measured at 40 1C. (8) Low-molecular organic compounds (fragrance ingredients) ϋϋ Use of odor-containing low-molecular organic compounds (fragrance ingredients) as an environmental material, KK-Matsuno et al. (J. Ajic.Food.Chem. 1992, 40, 1902-1905) for reference. The sequence is as follows. 1. Prepare a 0 · 3 sugar ether solution containing 1 0 0 ρ P m of various flavor ingredients (η-octane, η-octanal, η-octanol, ethyl hexanoate, d-limonene), As the test sample fragrance solution. 2. Fill the container with 700 ml of the test sample fragrance solution, cover it, and store it at 20 ° C for one month. 3. After one month, discard the test sample fragrance solution and use 60 ° The inside of the container was washed with distilled water of C and then dried. 4. Fill with diethyl ether and extract the fragrance component absorbed in the container. 5. Remove the diethyl ether from the container and add sodium sulfate anhydride to dehydrate it. 6. Pentylbenzene As an internal standard, quantitative analysis was performed with a gas chromatograph. As a result, when an aqueous solution containing 1 ppm of the fragrance component was present in the container, the fragrance component absorbed in the container was expressed. Therefore, the unit is wg / F > pm / |) 〇ttle [Experiment 1] A 700 ml polyethylene terephthalate resin container (PET resin made by Mitsui PET Resin Co., Ltd., type L125) was used as a plastic container and housed in the external electrode 12 of FIG. 1 and fixed. . This paper size applies to China National Standard (CNS) Α4 (210X 297mm) (Please read the precautions on the back before filling out this page)-, ιτ The consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs DU 493012 A7 B7 V. Description of the invention (1 6) Second, start the vacuum pump, external Inside the electrode 12 becomes 10 _ 4 t 〇rr After the vacuum (back pressure) at K, the flow rate of K 3 0 m 1. Mi ri is introduced into the argon into the plastic container, so that the pressure becomes 0. 4 t 〇rr. For pre-treatment, the inner surface of the R f electric plasma was treated with MW 300 W. After that, argon was used as an auxiliary gas to introduce Φbenzene, cyclohexane, benzene P-xylene, benzene or P- Xylene was used as the raw material gas in the container, and the inner surface of the container was evenly coated with DLC under the conditions shown in Figure 5. [Test results] Film thickness, film formation speed, density, adhesion 1, adhesion 2, alkali resistance The results of each evaluation are shown in Fig. 6. The density is more than 2.0 g / cm3, and the film (the system is very fine. The results of the square lattice test can show the adhesion with the polyethylene terephthalate resin. For good, it can be fully resistant to practical use. Also, alkali resistance is no problem, the film of DLC is extremely It can be understood that the polyethylene terephthalate resin can be completely protected. The results of the oxygen permeability, carbon dioxide permeability, and the degree of absorption of various perfume components are shown in Fig. 7. The delicate DLC film is not only completely inhibited The absorption of fragrance ingredients and effectively inhibits the transmission of carbon dioxide. Also shown in Figure 8 is the transmission spectrum in the ultraviolet visible light field of the trunk of a plastic container coated with SDLC film on the inside. From about 500 nm to about 500 nm In the ultraviolet range, the transmittance decreases sharply, which means that the coating of the DLC film can effectively suppress the degradation of the contents due to ultraviolet rays. Figure 9. Raman spectrum of a film coated on the trunk of a plastic container under the conditions of M test 1. This paper size applies to Chinese National Standards (CNS) Λ4 specifications (210X297 mm) 1 9 Shura ▼ Pack-(Please read the precautions on the back before filling this page) Order Φ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) 493012 A7 B7 V. Description of the invention (17) [Experiment 2] In addition to using 700 ml of polypropylene ♦ styrene copolymer resin container ( The product of Mitsubishi Monsanto Chemical Co., Ltd .: PAN resin, model L700) is used as the plastic container K, and the rest is the same as that of Test 1 to form a DLC film on the inner surface of the container. The conditions for forming the DLC film are as shown in FIG. 10. In the same manner as in Test 1, tests were performed on film thickness, density, adhesion 1, adhesion 2, alkali resistance, carbon dioxide gas barrier, oxygen barrier, and adsorption of low-molecular organic compounds. [Test results] The results of the tests on film thickness, density, adhesion 1, adhesion 2, and alkali resistance are shown in Fig. 11. Regarding the film thickness and density as shown in Equation 1¾, the situation is good. As for the adhesion 1 and the adhesion 2, if there is no problem in the test 1, the adhesion between the DLC and the polypropylene styrene copolymer resin is the same as that of the polyethylene terephthalate resin, and there is no practical use. problem. Fig. 12 shows the results of the degree of absorption of various perfume components, such as transmittance and carbon dioxide transmittance. That is, the gas barrier properties of polypropylene and styrene copolymer resins are inherently excellent. Furthermore, after coating with DLC, it became clear that the permeation amounts of oxygen and carbon dioxide reached extremely low levels. The absorption amounts of various perfume ingredients are the same as those in Experiment 1, and there is no problem in the sensory evaluation under the detection limit K. [Experiment 3] A DLC film was formed on the inner surface of the container in the same manner as in Experiment 1, except that a container made of a cycloolefin copolymer resin (product of Mitsui Petrochemical Co., Ltd .: COC resin model APL6015) with a capacity of 700 ml was used. Shape -20-(Please read the notes on the back before filling this page)
493012 87. Π· 1 6 五、發明説明(is 成 厚 膜 2 ο 性 示接 所 密 3 Ti , 圖丨 如 為 件 條 之 膜 度 密 性 接 就性 , 擋 法阻 方 氣 之 酸 1 碳 驗 試, 同 如 又 性 鹼 耐 試 行 實 wy S 分 性 著 吸 之 物 合 ]b 機 有 子 分 低 及 性 擋 阻 .氣 氧 驗 果 结 驗 試 结項 驗 驗 試試 之 個 性 一 鹼 耐何 , 任 2 性 2 接驗 密試 , 及 1i Ti 性 驗 接試 密同 , 如 度 。 密示 , 所 厚14 膜圓 於 如 關為 杲 著 吸 之 分 成 料 香 種 各 及 DL度 與過 器透 容碳 膠化 塑氧 是 二 其 , 尤 度 , 過 題透 問氧 無於 均II no 良 優 為 極 性 接 密 之 烯較 鐽比 為 量 脂著 樹 吸 物 份 合 成 聚料 共香 烴及 烯度 環 過 。 透 示碳 所化 15氧 圖二 如 , 為此DL 果 因 覆 结,塗 之 脂經 度 樹但 程 系 , 之烴大 準 水 之 低 當 相 HU 至 Ηϋ $ 抑 可 了 白 明 後 之 明 說 之器 號容 編 件 元 [ο 2 極 電 7\J- 葡 外493012 87. Π · 1 6 V. Description of the invention (is into a thick film 2 ο The properties show the dense 3 Ti, Figure 丨 If the film is tightly connected, the method is to block the acid 1 carbon The test is the same as that of the alkali resistance test. It is a combination of wy S and sexual absorption.) B The machine has a low sub-score and sexual resistance. He, any 2 sex 2 acceptance test, and 1i Ti sex acceptance test are the same, such as degree. Secret, the thickness of the 14 film is round, such as Ruguan is sucked and divided into different kinds of fragrance and DL degree and the device Permeable carbon gelled plastic oxygen is the second one, especially degree. The problem is that the oxygen is not equal to the average II no. Good is the polarity. The denser ene is higher than the ratio is the amount of resin. It is shown in Figure 2 that the carbon 15 is transformed into oxygen. For this reason, the DL causality is overlaid, and the fat longitude tree is painted, but the hydrocarbon system is large, the water is low, and the phase is HU to Ηϋ $. Ming Shuo Zhi Rong Rong Jian Yuan [ο 2 极 电7 \ J- Portuguese
立口 P --------_ (請先閱讀背面之注意事項再填寫本頁 經濟部中央標準局兵工消贽合作社印來Likou P --------_ (Please read the notes on the back before filling in this page. Printed by the Ordnance Disposal Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs
Ti 6 5 4 ri ii 1i ii i _ -1 件 置 搆 裝 緣 氣 ¥ ® ί源 板電管電孔 緣部氣頻出 0 内排高噴溝 立η 溝 本紙張尺度適川中國國家標準(CNS ) Λ4規格(210X 297公釐) 一 21 修正頁Ti 6 5 4 ri ii 1i ii i _ -1 pieces of structure edge gas ¥ ® ί source plate electric tube edge of the gas outlet frequency frequently 0 inline high spray ditch standing η ditch paper size suitable for Sichuan China National Standard (CNS ) Λ4 specification (210X 297 mm)-21 correction page
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JP6189224A JP2788412B2 (en) | 1994-08-11 | 1994-08-11 | Apparatus and method for producing carbon film-coated plastic container |
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EP (1) | EP0773167B1 (en) |
JP (1) | JP2788412B2 (en) |
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AU776224B2 (en) * | 1997-02-19 | 2004-09-02 | Kirin Beer Kabushiki Kaisha | Apparatus and method for manufacturing plastic container coated with carbon film |
US5879763A (en) * | 1997-09-03 | 1999-03-09 | Citizen Watch Co., Ltd. | Method of forming hard carbon film over inner surface of cylindrical member |
KR20010030823A (en) * | 1997-09-30 | 2001-04-16 | 테트라 라발 홀딩즈 앤드 파이낸스 소시에떼 아노님 | Method and apparatus for treating the inside surface of plastic bottles in a plasma enhanced process |
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-
1994
- 1994-08-11 JP JP6189224A patent/JP2788412B2/en not_active Expired - Lifetime
-
1995
- 1995-07-13 TW TW084107275A patent/TW493012B/en not_active IP Right Cessation
- 1995-08-09 AT AT95927997T patent/ATE226166T1/en active
- 1995-08-09 KR KR1019970700628A patent/KR100347249B1/en not_active IP Right Cessation
- 1995-08-09 DK DK95927997T patent/DK0773167T3/en active
- 1995-08-09 EP EP95927997A patent/EP0773167B1/en not_active Expired - Lifetime
- 1995-08-09 CA CA002196894A patent/CA2196894C/en not_active Expired - Fee Related
- 1995-08-09 WO PCT/JP1995/001583 patent/WO1996005112A1/en active IP Right Grant
- 1995-08-09 DE DE69528588T patent/DE69528588T2/en not_active Expired - Lifetime
- 1995-08-09 US US08/776,703 patent/US5798139A/en not_active Expired - Lifetime
- 1995-08-11 MY MYPI95002345A patent/MY113185A/en unknown
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JP2788412B2 (en) | 1998-08-20 |
KR970704607A (en) | 1997-09-06 |
EP0773167B1 (en) | 2002-10-16 |
WO1996005112A1 (en) | 1996-02-22 |
DE69528588T2 (en) | 2003-07-10 |
CA2196894C (en) | 2005-12-27 |
DK0773167T3 (en) | 2003-02-17 |
US5798139A (en) | 1998-08-25 |
JPH0853117A (en) | 1996-02-27 |
DE69528588D1 (en) | 2002-11-21 |
EP0773167A1 (en) | 1997-05-14 |
ATE226166T1 (en) | 2002-11-15 |
MY113185A (en) | 2001-12-31 |
EP0773167A4 (en) | 1999-08-18 |
KR100347249B1 (en) | 2003-03-10 |
CA2196894A1 (en) | 1996-02-22 |
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